Oxygen, water vapor, and carbon dioxide absorption in a single use container

ABSTRACT

The invention provides for a method of absorbing carbon dioxide comprising providing a container containing a product that gives off carbon dioxide, placing calcium hydroxide into the container, and sealing the container to form a sealed container.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part of U.S. patentapplication Ser. No. 13/028,740 filed Feb. 16, 2011, which is acontinuation-in-part of U.S. patent application Ser. No. 12/984,230filed Jan. 4, 2011, which is a continuation-in-part of U.S. patentapplication Ser. No. 12/751,583 filed Mar. 31, 2010, each of which isexpressly incorporated by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

None.

REFERENCE TO A “SEQUENCE LISTING”

Not applicable.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention primarily relates to the absorption of carbon dioxide andoxygen from a package containing a food product that emits carbondioxide and is degraded by oxygen.

2. Description of Related Art

In the packaging of foods, it is known that some food deteriorates byreacting with oxygen during the time it is stored. This has beenaddressed by evacuating packages to reduce and/or remove oxygen beforesealing, by coating foods with wax to protect them from oxygen in thepackage, and by lowering the temperature of storage to reduce the rateof spoilage. It is also known to utilize oxygen scavengers in thepackaging of vegetable and animal based food material. There has been aparticular interest in the preventing of oxidation of ground coffee asoxidation decreases the aroma and taste of the product. Freshly roastedcoffee emits significant quantities of carbon dioxide for a few daysafter roasting that, if not accommodated, can cause swelling of thepackage. Coffee has been vacuum-packed or packed in nitrogen to removeas much oxygen as possible at the time of packaging and to allow spacefor carbon dioxide.

Certain other foods and manufactured goods in addition to being degradedby absorbing oxygen also emit CO₂ either through respiration, baking, orroasting. Coffee, roasted nuts, cheese and certain electrical productsproduce a significant amount of carbon dioxide. Roasted coffee producersmust let coffee off-gas carbon dioxide prior to packaging or include avent so that the package will not swell and/or burst. The time that isnecessary to off-gas carbon dioxide also potentially allows volatileflavor compounds to escape. Employing a carbon dioxide scavenger willallow coffee to be packaged soon after roasting without accumulation ofcarbon dioxide gas. This lack of staging/exposure for off-gassing willnot only eliminate this economically negative processing time but willalso consequently result in retaining co-off gassing compounds/volatilesthat by their nature impart desirable characteristics of theorganoleptic profile of the coffee product.

There is also a problem with carbon dioxide swelling bags of other foodproducts, such as cheese that are also degraded by exposure to oxygen.Some cheeses that include live cultures, blue cheese being one example,benefit from the reduction of oxygen, but not to zero. Some oxygen mustbe retained to prevent the cultures in the cheese from dying.

Additionally, instant coffee and instant tea are quite aromatic andpleasantly so. Because these desirable flavor aromatics are volatile,any time lost between formation and packaging diminishes flavor andconsumer acceptance. A method of adsorbing CO₂ from within the packagewould allow instant coffee, instant tea, and other foods to be packagedsoon after roasting and preserve aroma and flavor.

In addition to ground coffee and leaf tea where residue of used coffeegrounds and tea leaves are present, there are substantially solublematerials to make hot and cold drinks that present similar storagedifficulties, that is, they are degraded by oxygen and emit carbondioxide. Instant tea, instant juices, and instant coffee may lose flavorand aroma as well as be subject to water absorption which will causeclumping or solidification of the material. Other hot drinks such ascocoa, grain beverages, and hot cold remedy beverages also suffer fromstorage difficulties. It would be desirable if these materials could bestored in such a way as to prevent their caking or agglomeration.Further, it would be desirable if such materials could be stored insingle use containers with protection from clumping and maintainingflavor and aroma while being ready for instant conversion to a beverage.

There is a need to provide oxygen removal, carbon dioxide removalsystem, and desiccant system which is relatively inexpensive and whichis sufficiently potent to remove oxygen, carbon, and water vapor frominstant and soluble beverage components.

In particular, there is a need for improvement in storage techniques forsingle use instant beverage containers. The single use containers arenot always subject to good inventory control and therefore may sit onshelves for a long period of time. Further, it is not economical topackage single use containers in sophisticated, very low oxygen, watervapor, or nitrogen atmosphere. Typically, single use containers haveabout 3-5% oxygen by weight in the atmosphere of the container and avarying content of water vapor during packaging and shipping.

There is need for more rapid absorption of carbon dioxide in order toprevent package swelling and flavor loss.

Many oxygen absorbers, particularly those based on transition metalssuch as iron, require moisture to effectively absorb oxygen. Iron is aparticularly effective oxygen absorber, but an electrolyte is needed forthe absorption to proceed rapidly. Coating iron particles with saltproduces a particle that can begin absorbing oxygen rapidly when wateror moisture is added.

BRIEF SUMMARY OF THE INVENTION

The invention provides a method of absorbing carbon dioxide and oxygencomprising providing a package containing a product that gives offcarbon dioxide, placing a carbon dioxide absorber that emits water suchas calcium hydroxide and an oxygen absorber that is promoted by thewater into the package, and sealing the package to form a sealedpackage.

Oxygen absorbers of the type with which this invention is concernedrequire water to react with the oxygen. Typically, oxygen absorbers haveeither been packaged with a source of water in the container, or havebeen packaged in a container that permits water vapor to enter thepackage. Neither of these approaches is ideal for products such ascoffee that benefit from a dry storage environment. Also, it isdesirable for the oxygen absorber to be present in the container, but tobe dormant until the food product is introduced. By using water createdby absorbing CO2, both of these problems are addressed.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 and FIG. 2 are top and side views of a container for use in theinvention.

FIG. 3 is a cross-section on line A-A of FIG. 2 of a prior artready-to-brew coffee container.

FIG. 4 is a cross-section of a single use container with a washer shapeabsorber.

FIG. 5 is an illustration of the invention utilizing a sachet containingoxygen scavenger or carbon dioxide scavenger, humidity regulator or acombination of scavengers and humidity regulators.

FIG. 6 is an illustration of the invention wherein a film havingabsorber properties attached to the lid of a single use container.

FIG. 7 is an illustration of the invention where a ring, strip, or beadof oxygen scavenger (or carbon dioxide scavenger, humidity regulator ora combination thereof) is placed at the bottom of the container.

FIG. 8 is a view of a carrier containing oxygen scavenger or carbondioxide scavenger, humidity regulator or a combination of scavengers andhumidity regulators in grooves.

FIG. 9 is a cross-sectional view of the invention carrier of FIG. 8.

FIG. 10 is a cross-sectional view of the carrier of FIG. 8 with absorberin the grooves.

FIG. 11 is a cross-section view of a carrier of FIG. 9 in a container.

FIG. 12 and FIG. 13 are top and cross-section views of a carrier with acup for containing absorber.

FIG. 14 is a cross-sectional view of a carrier with a sachet containingat least one of an oxygen scavenger, carbon dioxide absorber, or watervapor absorber.

FIG. 15 is a cross-sectional view of a ready to brew container with thecarrier of FIG. 14.

In FIG. 16 and FIG. 17 it is illustrated that the edges of the carriercould be irregular.

FIG. 18 and FIG. 19 illustrates another embodiment with a concavesupport having an integrally molded cup.

FIGS. 20, 21, and 22 are views of alternative bottom resting carrier ofthe invention.

FIG. 23 is a cross-sectional view of a container with the bottom-restingcarrier.

FIGS. 24 and 25 are graphs showing oxygen absorption in the examples.

FIGS. 26 and 27 are top and bottom views of a carrier of the invention.

FIG. 28 is a cross-sectional view of the carrier of FIG. 27 oncross-section line D-D.

DETAILED DESCRIPTION OF THE INVENTION

The invention has numerous advantages over prior practices in the art.The invention allows the formation of packaging systems where the activecomponent effectively maintains the freshness of the food or medicalproduct. The invention allows the formation of single serving containerswith an extended shelf life, while not changing the function or designof the containers. Further, the containers of the invention are low incost, and the containers of the invention further may utilizebiodegradable materials for the absorber and the container. The absorbermay be provided in a form that is particularly desirable for differentfood containers depending on their need for oxygen scavenging, carbondioxide scavenging, and/or moisture absorbing. These and otherembodiments of the invention will be apparent from the detaileddescription and drawings below.

The phrase “mammal ingestible” is intended to include humans, pets suchas dogs and cats, and farm animals. The container of the invention couldcontain snack drinks, medicine, and food products for non-human mammals.The non-human mammals could ingest the same or different materials asthe humans. While this disclosure relates to packages that areespecially useful for mammal ingested food, any food or other productthat emits carbon dioxide and is degraded by oxygen can benefit from theabsorber described herein.

The phrase “human ingestible material” is intended to include, amongother things, food, such as instant soup, instant coffee, instant fruitand vegetable juices, and instant tea; and medical products that may bedrank or ingested after being withdrawn from the container of theinvention. While water is the liquid normally used to dissolve orsuspend the human ingestible materials, other liquids compatible withhumans, such as juice or plasma, also could be used. Further, a flavoredwater or water enhanced with mineral or vitamins could be used. The term“sorbent” or “absorber” is used to indicate a material that absorbscarbon dioxide, oxygen, or water vapor by physical or chemical means.

The formation of single serving ready-to-brew coffee that is stored incups with lidding films is very successful. The containers used insingle serve ready to brew coffee are complex. They contain a filterthat holds the tea or coffee which is brewed by water passing throughthe top of the container and out of the bottom of the container. It isdesirable to form containers that fit the thousands of ready to brewsingle use coffee machines currently being used for formation of otherhot drinks. Costs could be lowered if the filter was eliminated. Manyother hot drinks could be formed from the containers at low cost if thefilter was not utilized in the container. However, as the injection ofwater and extraction of water in these machines is relatively rapid thematerials stored in the single use containers must be capable of beingrapidly dissolved or dispersed in the brief time the water is in thecup. Therefore, the materials need to maintain their particulatecharacter and not form agglomerates, clumps, or cakes that will not bereadily dispersed or dissolved. The invention provides for containerwith an absorber for materials that would have a deleterious effect onthe particular nature of materials in the cup without a filter.Generally, many mammal indigestible materials and human digestiblematerials will clump, cake, or agglomerate by the action of water vapor.The absorption of these gases in the container would also generally helppreserve the flavor and aroma of human indigestible materials dispensedutilizing the container. The taste is more consistent and the shelf lifeis longer.

The invention provides a cost-effective solution that does not requireredesign of the ready-to-brew containers. Coffee machines are designedto accept cups of known design and it is not practical to change thedesign of the cup. Further, it is desirable that biodegradable materialsbe utilized as the cups are discarded after one use. The humaningestible materials that do not need to be steeped in a filter includematerial such as instant coffee, instant tea, fruit and vegetablejuices, cold remedies, bullion, chicken broth, some narcotics, andcocoa. These materials may leave the container either as a solution or adispersion in the hot water.

FIGS. 1 and 2 show a top and side view of a prior art ready-to-brewcoffee container 10. The container 10 has a lid 12 and exterior sides14. During use, the lid 12 is pierced as is the bottom 16. Water isinjected through the lid 12 and coffee is removed from the bottom 16.Cross-sectional line A-A is generally through the center of thecontainer 10.

FIG. 3 is a cross-sectional view of a prior art ready-to-brew container10. The container 10 has a filter 18 that is sealed at 22 to thesidewall of the container 14. The ingestible material level in thecontainers is represented by M, and in use the lid 12 of the containeris pierced by means not shown and hot water is injected into thecontainer. The bottom of the container 16 is also pierced, by means notshown, and ingestible material in water is withdrawn from the bottom.The filter divides the cup into two spaces A and B. This inventionrelates to improvements in the ready-to-brew coffee containers as wellas other food and medicine containers in which no filter is present. Inthe invention structures like portions as in the prior art cup areidentically numbered as in FIG. 3.

FIG. 4 illustrates an embodiment of the invention where a washer-shapedabsorbent 72 is placed in a single use container. The washer-shapedabsorbent has a hole 74. The container will be pierced in the portion ofbottom 16 where the hole is located and the mammal ingestible fluid willdrain from the container 10. The absorbent washer is a polymer that hasthe absorbents for at least one of water vapor, oxygen, and carbondioxide mixed into the polymer prior to formation of the washer-shapedabsorbent 72.

The washer-shaped absorbent may be made with the techniques describedbelow. The washer and other shaped composite polymer and absorberarticles below also may be formed by the technique of U.S. Pat. No.7,595,278 to Powers, hereby incorporated by reference. Note, Examples 3and 4 of U.S. Pat. No. 7,595,278 disclose a moisture-absorbing compositematerial containing propylene and molecular sieve material.

FIG. 5 illustrates the cross-section of an embodiment in the inventionwherein a sachet 24 has been inserted into the container 10. This sachet24, which when oxygen absorption is desired, contains an oxygen absorber28 such as iron in combination with salt and electrolyte. The materialsin the sachet 24 will rapidly absorb oxygen during storage. The rapidabsorbing of oxygen is beneficial as instant coffee and cocoa also willabsorb oxygen, but the oxygen scavenger in the sachet is many timesgreater in rate of oxygen absorption than the instant coffee. Thesurface of the packet 26 is formed material that is vapor permeable butnot water permeable. It maintains its integrity above the temperature ofboiling water. The sachet 24 could be placed either on top of or belowthe material M in the container.

Alternatively or additionally, the sachet may contain a CO₂ absorbercapable of absorbing the CO₂ emitted from the instant coffee or instanttea thereby minimizing loss of flavor through volatilization. It is alsopossible that a carbon dioxide absorbing sachet could be used inaddition to the oxygen absorbing sachet. Water absorbing material couldbe in a sachet either alone or in addition to the other absorbers.

Alternatively or additionally, the sachet may contain a moistureregulating formulation capable of maintaining the water activity of theinstant coffee, cocoa, or other food product such as instant tea, at anoptimum level so that it is not too dry or too moist which can affectthe extractability of the flavor elements.

In a preferred form for rapid carbon dioxide absorption the sachet, orother container for carbon dioxide absorbing material, will contain acarbon dioxide absorber, such as calcium hydroxide in combination withsilica gel. The sachet may also include an oxygen scavenger/absorber,such as iron and/or any of the other oxygen scavenging materialsdescribed herein. Alternatively and/or addition, the oxygen scavengermay be disposed in an additional sachet separate from the sachetcontaining the carbon dioxide absorber. At least a portion of the wallof the sachet or other container is permeable to carbon dioxide. It hasbeen found that calcium hydroxide absorbs carbon dioxide much fasterthan the conventionally used calcium oxide. Calcium oxide will behydrolized to form calcium hydroxide which will absorb carbon dioxide.However the delay in acquiring water and reacting with water to formcalcium hydroxide is avoided if the carbon dioxide absorber is initiallycharged with calcium hydroxide. The calcium hydroxide is granular form.In a preferred form the package contains between 38 and 66% by weight ofcalcium hydroxide when it is combined with silica gel. In the preferredratio about 100 cm³ of carbon dioxide is absorbed per gram of thecalcium hydroxide and silica gel blend. The ratio of silica gel tocalcium hydroxide will be maintained even if oxygen absorbers and orwater absorbers are also present in the container.

A suitable particle size of calcium hydroxide is between 0.5 and 100microns. A preferred particle size of calcium hydroxide is about 1-20microns as this has low-cost and will provide good flowability formanufacturing. The grain size of the silica gel is selected to providethe desired good dry flow characteristics when combined with the calciumhydroxide. Generally a silica gel size of between 0.5 and 100 microns ispreferred because of good full flow when mixed with the calciumhydroxide. In such embodiments, a water vapor absorber, such as disodiumoxide, calcium oxide, silica gel, molecular sieve, and/or other moistureabsorbent materials described herein absorbs water which is a product ofthe absorption of the carbon dioxide by the calcium hydroxide.Alternatively, as will be described in greater detail below, the waterproduced by the carbon dioxide absorber as a result of the absorption ofcarbon dioxide at least partially promotes the oxygen scavenger Calciumhydroxide is less expensive than the calcium oxide which has been usedin the prior art. The handling of calcium hydroxide grains is alsosimilar to the handling of the previous calcium oxide. Therefore, theuse of calcium hydroxide provides the benefit of faster carbon dioxideabsorption activity without increasing cost of the product.

While described as utilized with in sachet such as illustrated in FIG.5, it is also possible that the carbon dioxide absorber and/or theoxygen scavenger could be utilized in other forms, such as embedded in apermeable film, extruded in a gas permeable polymer as a ribbon or film,or placed into an at least partially permeable container. Variousmethods of containing the carbon dioxide absorber are disclosed herein.In any of these methods of using or packaging the calcium hydroxide willprovide more rapid absorption of carbon dioxide than calcium oxide. If aslower absorption of carbon dioxide is desired then calcium oxide may beutilized successfully.

The sachets, ribbons or containers containing calcium hydroxide forcarbon absorption may be shipped in source supply containers. The sourcesupply containers further contain an inner ceiling bag of substantiallyair and carbon dioxide impermeable polymer sheet. Depending on the typeof manufacturing utilizing the calcium hydroxide carbon absorbers theymay be in the form of sachets, ribbons, or containers having at leastone permeable side. Further the sachets may be linked together in a roleand severed immediately prior to use.

Accordingly, an example method of absorbing carbon dioxide using one ormore of the sachets 24 and/or containers 10 described herein may includedisposing a carbon dioxide absorber and an oxygen scavenger within acontainer 10 containing a material M or other like product. The productmay be disposed within, for example, an inner cavity of the container,and such an inner cavity may be a substantially empty space,compartment, or other like portion of the container 10 configured toreceive the product. For example, the inner cavity may comprise asubstantially empty space formed by (i.e., substantially surrounded by)the bottom 16 and sidewall 14 of the container 10. In embodiments inwhich the container 10 is substantially cylindrical, the inner cavitymay comprise a substantially cylindrical space within the container 10extending upward from the bottom 16 to the lid 12, and bound by thesidewall 14. In other embodiments, however, the inner cavity may haveother configurations as defined by the sidewall 14, the bottom 16,and/or the lid 12.

The product may comprise any of the mammal ingestible materials, humaningestible materials, and/or other products described herein. In suchembodiments, the product may give off, for example, carbon dioxide as isknown with ground coffee, or other like products. Additionally, theproduct may be degradable in the presence of oxygen. Thus, it may beadvantageous to reduce and/or substantially eliminate the amount ofoxygen within the container 10 so as to prolong the freshness and/orusability of the product. It may also be advantageous to absorb thecarbon dioxide given off by the product to maintain the integrity of thecontainer 10 once the container 10 is sealed with the product isdisposed within the container 10. For example, absorbing the carbondioxide given off by the product may prevent a sealed container 10 fromrupturing or otherwise failing.

Such example methods may also include sealing the container 10 to form asealed container 10 containing the carbon dioxide absorber, the oxygenscavenger, and the product. For example, after the carbon dioxideabsorber, the oxygen scavenger, and the product have been disposedwithin the container 10, the lid 12 may be heat-sealed, adhered, and/orotherwise connected to the container 10 such that a substantiallyfluid-tight seal is formed between the lid 12 and the container 10.While disposed within the container 10, the product may emit carbondioxide. Thus, such an example method may include absorbing, with thecarbon dioxide absorber, carbon dioxide given off by the product withinthe container 10. In such methods, absorption of the carbon dioxide bythe carbon dioxide absorber may produce water. In some embodiments, thewater produced during the absorption of carbon dioxide may be in theform of water vapor.

In example embodiments, the sachet 24 may be formed from at least one ofa carbon dioxide permeable material, an oxygen permeable material, and awater vapor permeable material to facilitate the absorption of carbondioxide, oxygen, and/or water. Additionally, the container 10 may beformed from any of the polymers or other materials described herein, andmay have any desired permeability characteristics. For example, thecontainer may be formed from a material such as polyethylene,polypropylene, or other like polymers, and such materials may besubstantially impermeable to carbon dioxide, oxygen, and water in bothliquid and/or gaseous form.

If keeping the environment within the package free from water or watervapor, is important the absorber may be packaged in a material that ispermeable to carbon dioxide and oxygen, but impermeable to water vapor.This would allow an absorber to be produced that doesn't require anyexcess moisture and is promoted by absorbing carbon dioxide rather thanwater vapor.

Such an example method may also include at least partially promotingoxygen absorption by the oxygen scavenger disposed within the containerby using the water produced during the absorption of carbon dioxide.Preferably, the carbon dioxide absorber is disposed with respect to theoxygen absorber so that the water created by the carbon dioxide absorberis available to the oxygen absorber to facilitate the absorption ofoxygen. This availability of water to facilitate the absorbtion ofoxygen is what is meant by the terms “promote” or “promotion.”

In such embodiments, the water vapor absorber or other like componentsdescribed herein may be omitted. Thus, using the water produced duringthe absorption of carbon dioxide to at least partially promote theoxygen absorbers activity may reduce the cost and complexity ofmanufacturing sachets 24 of the present disclosure.

Even more preferably, the oxygen absorber can be a finely divided metalpowder such as iron that is coated with a halogen salt such as sodiumchloride. Such coated particles absorb oxygen very slowly at best untilwater is available to form an electrolyte which greatly enhances thespeed of oxygen absorption. Upon promoting the oxygen absorptionreaction, the oxygen scavenger may begin absorbing oxygen within thecontainer 10, thereby maximizing the useable life of the product.

In order to create an effective version of this absorber, it isimportant to consider the amount of carbon dioxide that is needed to beabsorbed. From this, determining the amount of material needed to absorba given amount of carbon dioxide, the amount of water produced, andtherefore the maximum amounts of iron that can be oxidized and oxygenthat can be absorbed is easily done to stoichiometry.

For the absorption of carbon dioxide, calcium hydroxide absorbs carbondioxide to produce calcium carbonate and water based on the followingequation:

Ca(OH)₂+CO₂CaCO₃+H₂O

That is, in order to absorb one mole of carbon dioxide, one mole calciumhydroxide is needed which produces one mole of water

For the absorption of oxygen, there are multiple paths for the oxidationof iron, however, the most complete is described as:

4Fe+3O₂+6H₂O→2(Fe₂O₃+3H₂O)

From this it is apparent that to absorb three moles of molecular oxygen,it requires six moles of water and four moles of iron, or moresuccinctly 1.5 moles of water is required to oxidize one mole of ironwith 0.75 moles of oxygen.

As illustrated above, one mole of calcium hydroxide produces one mole ofwater when it reacts with one mole of carbon dioxide. From this, it isapparent that 1.5 moles of carbon dioxide can be absorbed by 1.5 molesof calcium carbonate to produce 1.5 moles of water which will react witha maximum of one mole of iron to absorb a maximum of 0.75 moles ofoxygen. From this is easy to work out the amount of material needed toabsorb a given amount of oxygen or carbon dioxide, or to determine howmuch carbon dioxide or oxygen can be absorbed from a given material.

Is important understand that the moles of iron represent the maximumamount of iron that can be reacted with the amount of water produced.This reaction could be slow. Additional water and a salt or the like maybe required to create electrolytes to accelerate the oxidation reaction,therefore reducing the total amount of water available for the oxidationreaction itself. An additional consideration is that instance is that ifthere is too much water, the oxidation reaction could actually bequenched or more seriously the excess water can reach out theformulation and potentially contaminate the product is trying toprotect.

While these calculations are all done in moles is very easy to convertthese into grams. The critical molar masses are included in thefollowing table:

Compound Molar mass Calcium hydroxide 74.093 g/mol  Carbon dioxide 44.01g/mol Water 18.015 g/mol  Iron 55.85 g/mol Molecular oxygen 31.99 g/mol

The methods described above may be employed with any of the containersdescribed herein. Additionally, although the above methods have beendescribed in relation to the use of a sachet 24, in further embodiments,such methods may also be used in conjunction with the various films,ribbons, carriers, cloths, tablets, rings, or other structures describedherein. For example, in additional embodiments, one or both of thecarbon dioxide absorber and the oxygen scavenger may be embedded in afilm or other like structure, and the film may be disposed within theinner cavity of the container 10. Alternatively, the film may be adheredto, embedded within, and/or otherwise connected to the sidewall 14and/or the lid 12.

In the embodiment of FIG. 6, the container has been provided with anabsorber film 29 that is adhered to lid 12. The absorbent film would beadhered to the lid material 12 prior to the lid being placed on to thecontainer. The film may be cast, laminated or extrusion coated onto thelid or preformed and attached to the lid by adhesives, ultrasonicsealing, or heat sealing. This embodiment has the advantage thatabsorber film is added to the lid prior to the packaging of the mammalingestible material. The absorbent film 29 may consist of multilayerstructure in which the absorber is in the inner layers of the structure.The film may be provided with an abrasion resistant layer or a slipperylayer, not shown, that will provide abrasion resistance or slippage sothat the mammal ingestible material will not be able to remove theoxygen, carbon dioxide, and/or oxygen absorbent (scavenger) materialsfrom the film. The resistance or slippage layer may be formed ofpolyethylene, polypropylene, polyamide and their copolymers.Conventional slip additives may be added into the layer that contactsthe mammal ingestible material to result in a coefficient of friction of0.5 or below, preferably 0.3 or below. The film may be an oxygenabsorbing film, it is also possible that the film only contain CO₂absorbing materials or only water vapor absorbing materials. It isfurther possible that it contain any combination of carbon dioxide,water vapor, and oxygen absorbing materials.

In the embodiment of FIG. 7, the oxygen scavenger or other absorber isplaced on the bottom 16 and the bottom edge 34 of cup 10. The scavenger32 may be placed there by a variety of techniques, but an extrusiontechnique, such as utilized for hot melt adhesive would be quick andcould be done during manufacturing prior to filling the container 10. Apreformed scavenger ring of sorbent film also could be attached to thebottom interior edge 34 of the cup. Placement of the sorbent also couldbe performed by other extrusion coating methods. The extrusion materialsinclude hot melt polymers as well as plastisol materials that would curein place.

FIGS. 8 and 9 are a top view and a cross-sectional view of a carrier forabsorber 23 for use in the container of the invention. The support hasgrooves 29 and 33. The support further is provided with a hole 41. Inthe cross-sectional view of FIG. 8, carrier 23 has been provided with agas permeable, water impermeable cover sheet 35. Further, the grooves 29and 33 are then filled with at least one of particulate oxygen scavengermaterial, carbon dioxide absorbent material, and water absorbentmaterial. In FIG. 10 is illustrated the carrier 23 with grooves 33 and29 filled with particulate absorber 29. The absorber 29 and carrier 23are then covered with a sheet of material that is impervious to waterbut will pass gases such as oxygen and carbon dioxide. After placementon the carrier, the sheet is cut away to open the hole 41 if the sheethas not been previously cut to size. This embodiment allows the use ofparticulate absorber.

FIG. 11 illustrates the cross-section of an embodiment in the inventionwherein a carrier 23 has been inserted in container 10. This carrier 23contains an oxygen absorber 45 such as iron in combination with salt andelectrolyte in grooves 29 and 33. The grooves 29 and 33 are covered bygas permeable and liquid water impermeable film or cloth 35. The centerhole drain 36 provides for draining of the human ingestible material.Drain hole 41 is not covered by the permeable film. The materials in thegrooves 29 and 33 will rapidly absorb oxygen, carbon dioxide, or watervapor during storage. The rapid absorbing of oxygen is beneficial ascocoa and instant coffee also will absorb oxygen, but the oxygenscavenger in the carrier 23 is many times greater in rate of oxygenabsorption than the instant coffee. The surface film 35 is formedmaterial that is vapor permeable but not water permeable. It maintainsits integrity above the temperature of boiling water.

FIGS. 12 and 13 illustrate a carrier 40 that contains a cup 42 in thehole 41 of the carrier. The carrier 40 is provided with a multiplicityof small drain holes 44. The carrier 44 is provided with a cup 42 thatfits into the hole 41. As shown in FIG. 13, the carrier has a cup 42which is covered with a gas permeable cover 48. The cup contains atleast one of a particulate oxygen scavenger, carbon dioxide scavenger,and water vapor absorber 46. The gas permeable film or cover may beformed of a gas permeable film or bonded fiber material such as Tyvek orGore-Tex. In FIG. 14, there is illustrated a carrier containing a cup42. A sachet 54 that contains particulate absorbent is in cup 42. Thesachet is formed of a permeable film or fabric. In FIG. 15, there isillustrated the support 40 utilized in a single use container of theinvention.

The carrier 40 is designed to be held by gravity in the single usecoffee container 10 which narrows towards the bottom 16. It is alsopossible that a stop could be molded into the side of the container onwhich the carrier would rest. It is also possible that the carrier 40could be held in place by adhesive. Further, it is possible that thecarrier could be provided with a jagged edge or wavy edge to aid indraining of the coffee from a single use container. FIG. 16 is anillustration of a wavy edge of a carrier 58. FIG. 17 is an illustrationof a jagged edge of a carrier 62. It is also desirable that the groovedcarrier 23 be perforated to aid in drainage. The perforation wouldnormally need to be accomplished after the grooves have been filled andcovered.

In FIG. 18 is illustrated a concave carrier 64 that has the cup 42integrally molded with the carrier 64. The concave carrier 64 issuspended in the package so as to be concave when viewed from the top ofthe package. A concave carrier may aid in centering of the carrier inthe container. In the top view of a carrier such as 64 in FIG. 19 showsmultiple large drain holes 66 for the liquid human ingestible materialto pass through. The cup 42 may be covered with fabric after filling theparticulate matter. Alternatively, the cup could contain a sachet,capsule, or polymer member comprising scavengers and/or absorbents. Thecup further could have a snap fit gas permeable and liquid impermeablelid.

In FIGS. 20-22 is shown in the embodiment of carrier 70 of the inventionwith slots 72 for drainage. FIG. 21 is a top perspective view of thecarrier and FIG. 22 is a bottom perspective view. The carrier 70 isdesigned to sit on the bottom of the container with the bottom 76 of theouter ring 78 on the bottom 16 of the container. The upper surface ofring 78 is surface 77. The cup 42 may have a gas permeable film attachedto surface 82 to seal in an absorber or scavenger that has placed in cup42. A snap cap of vapor with permeable material is a preferredembodiment. Cup 42 is provided to contain at least one of the oxygenscavenger, carbon dioxide absorber, water absorber or other treatmentmaterial for human ingestible material. A cap 82 for cup 42alternatively may be welded to cup 42, snapped in place, or adhesivelyconnected. The carrier 70 further could be made with an opening and havea preformed can of treatment material bonded in place, preferably byspin welding. A gas permeable snap on cap 82 for the cup 42 is preferredfor ease of formation of the carrier.

FIG. 23 is a cross-section of a container using the carrier 70. Asshown, the carrier 70 rests on the container bottom 16 with surface 76of the carrier. The cup 42 has permeable cap 82. The cup 42 containsabsorbent members 84. The carrier 70 does not interfere with piercingthe middle of the bottom of the container 10 for drainage.

While the above illustrations have shown particulate absorbents it isalso possible that the absorbents could be incorporated into a plasticfilm, placed in a permeable capsule or pressure formed into a tablet.The tablet then may be covered with a gas permeable film or coating. Thetablets, pieces of film, extruded polymer, or sachet as illustratedcould be it in the cup of the carrier.

The cup 42 is shown as a separate member that is inserted into thecarrier 40. The cup may be held in the carrier by spin welding,ultrasonic welding or pressure fitting. However, the cup in anotherpreferred embodiment could be integrally molded with the absorbercarrier. Further, it is possible that the carrier itself could be formedof a polymer that contains at least one of oxygen scavenger, carbondioxide absorber, and dehumidifier material. If the support itself wasformed of a material that absorbs oxygen and/or carbon dioxide it wouldonly be necessary to form holes in the support for drainage and/or haveirregular edge on the carrier. No cup would be necessary. Further, whilethe cup is illustrated in substantially the same height as the thicknessof the support in several embodiments, it can be made deeper in order tohold more absorbents. Further the cup could be closed by a plug or afitted cover. The cup also could be a preformed gas permeable can thatis bonded to the carrier.

FIGS. 26, 27, and 28 illustrate carrier 90 in an embodiment of theinvention. Carrier 90 in FIG. 26, which is a top view, has a reinforcingring around hole 92. The carrier 90 has a foraminous area 102 that hasholes 96 separated by pieces of polymer 104. The holes that are in theforaminous portion 102 are numerous leaving just enough polymer 104 tosupport the conical shape. In use, carrier 90 sits on the bottom of thecup on the lower ring 98. The carrier is convex as seen from the top ofthe container. When forming a preferred carrier for water vaporabsorption, the preferred polymer is propylene blended with calciumoxide and/or molecular sieve material. The carrier 90 also could beutilized for oxygen or carbon dioxide absorption with absorbers of thesegases in the polymer.

It is possible to utilize material containers for ingestible drinks thatare quite permeable to gases such as oxygen, water vapor, and/or carbondioxide. The containers are then sealed inside a bag that is impermeableto oxygen and carbon dioxide and water vapor. The bag has oxygenabsorbers and/or carbon dioxide absorbers and/or water absorbers placedinto the bag before it is sealed. The bag is opened immediately beforeuse so that the ingestible drink such as cocoa does not lose freshnessbefore use. Absorbers in the cup would prevent deterioration after thebag is opened and the individual containers are stored until use. Thepermeable container may be formed of a biodegradable material, such aspoly lactic acid (PLA) or a copolymer of PLA and another polymer such aspolyethylene or an acrylic. Alternatively, the cups could be formed of athin, low cost or very thin polymer, permeable to oxygen, carbondioxide, and water vapor. The bag may be foil, polyvinyl alcohol, orhigh-density polyethylene, preferably in layers that allow the bestbarrier property to be achieved in the bag.

Any suitable resin may be utilized in the invention for the polymer thatholds the oxygen scavenger or other sorbent. The polymer holds thesorbent so that it will not be carried into the coffee or other foodproduct when the container is used, but allows gas to reach theabsorbent. Polymers useful for making the oxygen scavenging andabsorbent articles can include common polyolefins such as low-densitypolyethylene (LDPE), high-density polyethylene (HDPE), polypropylene(PP), polystyrene (PS), high impact polystyrene (HIPS), polycarbonates(PC), poly(methyl methacrylate) (PMMA) and their derivatives orcopolymers.

Polymers suitable for the invention and biodegradable include commonpolymers generated from renewable resources and biodegradable polymerssuch as polylactic acid copolymers, starch based polymers such asthermoplastics starch, polyhydroxyalkanoate (PHA), polyhydroxybutyrate(PHB). Biodegradable polymers that are petroleum based such aspolyethylene oxide and polyvinyl alcohol (PVOH) are also included.

The invention uses common plastic article fabrication processes thatinclude extrusion, injection molding, extrusion coating, lamination,tableting and compounding to form the sorbent structures includingoxygen scavengers, CO₂ absorbers, and moisture regulators.

While the invention is discussed with respect to the utilization of afood container for instant coffee, instant tea, and cocoa, the conceptsand container of the invention are also suitable for other uses. Thecontainers disclosed would be suitable for use in other food productswhere water or other liquids are added to the material contained in thecontainer and wherein a changed liquid is withdrawn after dissolving ordispersing the food product. Typical of such materials would be tea,soup, milk components, and soup broth. The containers also could be usedfor medical products that are shipped as solid particles or areconcentrated and then a carrier liquid is passed through the cup andthrough the concentrated liquid or solid particles to result in amedicinal liquid. An example of this would be drugs, such as powderednarcotics, such as morphine and methadone hydrochloride, and materialsutilized as radiology tracers. They could also be used for alcoholicmixers.

The calcium hydroxide utilized for absorption of carbon dioxide may beutilized as discussed in the previous paragraph. Further the calciumhydroxide may be utilized in absorption of carbon dioxide from otherfood materials that are not packaged for dissolving in a fluid. Thesewould include food materials such as cheese, kimchi, coffee, and anyfermented product. The calcium hydroxide products for carbon dioxideabsorbers also may be utilized for absorbing carbon dioxide given off byelectrical products. The calcium hydroxide materials may be utilized asa preferred material for any storage where rapid absorption of carbondioxide after packaging is desired.

The invention method of placing scavenger materials in a container, asstated above, could be used for packaging of products that are sensitiveto moisture. Such products include many medicines and food products.Such food products as flour, drink mixes, gelatin desserts, and salt orother seasonings are subject to deterioration if moisture is present inthe container. Moisture absorbent materials such as disclosed in U.S.Pat. No. 5,322,701-Cullen, herein incorporated by reference, could beplaced into containers to enable longer storage of such materials.Suitable moisture absorbent materials include calcium oxide, silica gel,molecular sieve, and cellulose fibers.

The following are methods for making a solid oxygen absorbingcomposition or coating for use in the invention.

The oxygen scavenger may be in the form of a powder blend in a sachet ora pressed solid formed from compressed particles and binder. A method ofmaking a compressed or pressed oxygen absorbing disc, tablet, wafer,washer, or capsule is as follows. Forming a blend of powdered absorbentbased on iron powder with sodium chloride as an electrolyte, silica gel,and a binder that does not need to be heated very high in temperature.The binder can be a fine powdered polyethylene that will soften whenunder a pressure of between 3,000-50,000 pounds per square inch. Thecomposition can also be heated to set or cure the binder but it cannotbe heated above the boiling point of water to keep the moisture in thecarrier. A suitable composition by weight would be about 18%polyethylene, 40% iron powder, 30% silica gel, 8% water and 2% sodiumchloride. It is best to use a resin binder with a softening point abovethe boiling temperature of water.

A method for making an oxygen absorbing compound would be to put theoxygen absorbing composition in a thermoplastic material so that theoxygen absorbing compound could be filled into a container as a liquidring and allowed to set or harden. This composition would be by weightabout 40% thermoplastic resin, 30% iron powder, 20% silica gel, 9% waterand 1% sodium chloride. An additive, such as CaCO₃, clay, or talc, couldbe used to increase the porosity of the resin and to increase the rateof oxygen absorption. This absorbent composition could be deposited intoa container or made into a tape that could be put onto the inner sidesof the container. The thermoplastic resin can be a vinyl acetate, ethylvinyl acetate, polyurethane or combinations thereof.

Another method for making an oxygen absorbing composition is dispersingthe oxygen absorbing composition into a polyvinylchloride plastisol.These plastisols are used as cap liners and as gaskets in caps and jarlids. This oxygen absorbing plastisol composition may then be put intothe cup as a liner, a ring or coating along the sides or bottom edge ofthe cup. This composition would be semi liquid and could be placed intothe cup and allowed to set. The plastisol may be selected fromhigh-density polyethylene, high density polypropylene, acrylic vinylacetate ethylene copolymer, ethylene vinyl acetate, vinyl acetatehomopolymer, acetate ethylene copolymer, plasticized vinyl chloride,oxidized polyethylene homopolymer and polyurethane. The preferredplastisol is polyvinyl chloride as it does not react with foods and isresistant to the temperature of boiling water. The oxygen absorptioncomposition can be up to 75% by weight with the other 25% being thepolymer. One composition was 10.35 grams of polyvinylchloride plastisol,12.51 grams of iron powder containing 2% by weight sodium chloride.

Illustrative of a plastisol material is polyvinyl plastisol in an amountof 10.35 grams was blended with 12.51 grams of 200 mesh iron powdercontaining 2% by weight sodium chloride. The blending was done with anelectric high-speed mixer. A sample of the resulting composition wascoated onto a container cap. The rate of oxygen absorption was measuredover time.

Sample 1 Sample 2 Sample 3 Sample 4 Composition weight 1.47 grams 1.71grams 1.51 grams 1.56 grams CC of oxygen absorbed after 22 10. 10. 10.10. hours CC of oxygen absorbed after 46 15. 14. 15. 15. hours CC ofoxygen absorbed after 96 24. 22. 24. 23. hours CC of oxygen absorbedafter 184 37. 32. 37. 35. hours CC of oxygen absorbed after 234 37. 32.37. 35. hours CC of oxygen absorbed after 330 51. 41. 48. 47. hours

The test vessel contained 500 cc of air or 100 cc of oxygen. The testwas conducted at room temperature with a moisture source in the testvessel.

Another invention composition would be to disperse the sorbentcomposition in a multiple component carrier such as an emulsion,dispersion, suspension or other mixtures. By dispersing the sorbent insuch a multi component system the resulting composition can be moreeasily applied to a cup as an oxygen scavenger or sorbent coating. Thesetypes of coatings can contain more of the oxygen absorbing compositionand have greater permeability for oxygen. By not fully drying the waterbased systems we can have a self-promoting and self-reacting oxygenabsorbing coating. Glucose oxidase can be used in place of the iron. Axanthan gum emulsion, alginate emulsion or microcrystalline cellulosesystem can also be used. This system can also contain water in the ironbased oxygen absorbing system. Adhesive based emulsion can also be usedsuch as acrylic polymer emulsions in water, a polyvinyl acetate in wateremulsion, and a vinyl acetate ethylene copolymer in water emulsion canbe used. The oxygen absorbing composition would be an iron powder withsodium chloride as an electrolyte and a moisture carrier. The moisturecarrier can be silica gel, hydrogel or any other moisture carrier thatcan hold moisture. In oxygen absorbers, it is also possible to not fullydry the moisture out of the emulsion thereby leaving some moisture inthe coating. An alginate gel would be by weight percent 2.25% sodiumalginate, 1.0% polysorbate 80, 0.2% sodium propionate and 96.55%distilled water. A xanthan gum emulsion would be by weight 2.0% xanthangum, 43% isopropyl alcohol and 55% water. These two emulsions could becombined 1 part emulsion with 1 part oxygen absorbing compositioncomposed of 99% iron powder and 1% sodium chloride as the electrolyte.The oxygen absorbing composition can be a fine iron as fine as 2-5microns in particle size to improve the clarity of the oxygen absorbingcoating or oxygen absorbing compound. A thin film layer or coating canbe put over the final coating to insure that no oxygen absorbingingredients or sorbents migrate out over time. This thin film cover cana cellulose acetate polymer, vinyl acetate ethylene copolymer, vinylacetate homopolymer, acetate ethylene copolymer, plasticized vinylchloride polymer, acrylic polymer or an oxidized polyethylenehomopolymer.

The water absorbers and carbon dioxide absorbers may be placed into thepolymer by a substitute for the oxygen absorbers. The preferred watervapor absorbers are silica gel and molecular sieve materials.

Any suitable transition metal, typically including zinc, copper, iron,cobalt and zirconia, may be utilized in the oxygen scavenger of theinvention. The preferred oxygen scavenger of reduced iron powderpreferably has 1-200 um mean particle size, more preferably 5-50 um meanand most preferably 10-40 um mean. The iron can be mixed with salt or acombination of different electrolytic and acidifying components. Theiron particles can, in a preferred embodiment, also be coated withelectrolyte salt. The combination and relative fraction of promotingelectrolytic and acidifying components coated onto the iron particlescan be selected according to the teachings of U.S. Pat. No. 6,899,822and co-assigned published U.S. Patent Applications 2005/0205841 and2007/020456, incorporated herein by reference. The coating technique ispreferably a dry coating process as described in the references above.

The salt can be any salt such as sodium, potassium or calcium basedionic compounds that are soluble in water. Typical examples includeNaCl, KCl, Na₂HPO₄ and others. A mixture of separate electrolytic andacidifying salt components can be advantageously used in the formulationas described in prior art. Sodium chloride is preferred because it iseffective and low in cost.

The oxygen scavenging fabricated article may contain moisture regulatorsbased upon silica gel, molecular sieve, activated carbon, clay or otherminerals. The compounds may contain various levels of water to achievewater activities ranging from 0.01 to 0.85.

The film/tape/ribbons/wafers/washers used in the invention may be asingle or multilayer films that are porous or solid, and consisting ofiron-based oxygen scavengers and electrolytes, such as disclosed inco-assigned U.S. patent application Ser. No. 12/416,685, filed Apr. 1,2009, hereby incorporated by reference and U.S. Patent Publication No.2010-0255231, published Oct. 7, 2010, also hereby incorporated herein byreference. The film optionally consists of moisture regulators with achosen water activity. The film may be in circular or strips that can befitted into a container as a bent strip. Multilayer film is preferredwith oxygen scavenger or other absorber embedded inside the film and notexposed on film surface. Films with some porosity or voids are preferredto facilitate the rate of oxygen, carbon dioxide, or water vaporabsorption. Moisture regulator can be incorporated into the film duringextrusion or from post-extrusion processing. The films can be laminatedto the lids or container sides.

The insert may be a ring shaped oxygen scavenging article as in FIG. 4with a ring diameter smaller than the bottom of the container such thatthe insert can be laid flat inside the container. The insert can befabricated by die-cut from the films above or by other fabrication meanssuch as injection molding and compression molding.

In the embodiment using strands/paste, such as in FIG. 7 or in cup 42, asection of elongated or shaped oxygen scavenging material that consistsof oxygen scavenger, salt and moisture regulators may be utilized. Amethod of making such a strand is by melt extrusion. The polymer may bepolyethylene, wax, polyethylene glycol, cellulosic polymers, polylacticacid, and starch-based copolymers. The moisture regulator may be salts,silica gel, clay, molecular sieve or like that contains certain levelsof moisture.

A method to remove CO₂ in the package is described as follows: using ascavenger specifically designed for CO₂ absorption. A packet made of agas permeable polyolefin film containing carbon dioxide absorbingparticulates is packaged in a single use container to absorb theoff-gasses. The preferred packet will have high gas permeation and lowwater vapor permeation properties. The absorber will be capable ofabsorbing a high concentration of CO₂ and not interfere with thearomatics components of the human ingestible material. The CO₂ absorbercan contain certain amount of calcium hydroxide, silica gel and water,with other ingredients. Optionally calcium hydroxide may be replacedwith other hydroxides such as sodium hydroxide and potassium hydroxideor mixtures of these and other hydroxides. Optionally, alkaline,alkaline earth or metal oxides may be used in conjunction with orreplacing hydroxides. The oxides include but not limited to calciumoxide, aluminum oxide and magnesium oxide. These oxides may be used inmixture format. For reference, the range and formulations useful as CO₂absorber are described in U.S. Pat. No. 5,322,701 assigned to MultiformDesiccants, Inc., hereby incorporated by reference.

As described for the oxygen absorbing materials above the oxygen andcarbon dioxide scavenging formulations may be packaged in a format otherthan a packet. The carbon dioxide scavenging formulations may beenclosed in oxygen or carbon dioxide permeable capsule or a tablet thatmay be coated with a permeable or semi-permeable polymer material. Anyresin or polymer permeable to oxygen and/or carbon dioxide may be usedto coat the tablets. Water base polymer coating of the tablets ispreferred. Preferred coating polymers are hydroxylpropylmethyl-cellulose or acrylic water base coatings. They may also befabricated in a compact form, such as a washer, wafer, disc or platelet,wrapped with a coating or polymer film that is gas permeable orsemi-permeable. The coating method of making the disc, platelet ortablet can include dip coating, spray coating, flash coating, spincoating or any other known methods that are applicable to forming theproduct. The film method can include overcoating, lamination, multilayerlay up followed by die-cutting, and any other known methods that canmake film composite layered articles. The methods of forming oxygenabsorbents above may be used for forming sorbent materials for CO₂absorbents and water vapor absorbents.

Alternatively or additionally, the sachet, grooves, film, or cup maycontain a CO₂ absorber capable of absorbing the CO₂ emitted from thecoffee permitting it to be packaged a short time after roasting therebyminimizing loss of flavor through volatilization. It is also possiblethat a carbon dioxide absorbing sachet could be used in addition to theoxygen absorbing sachet.

Alternatively or additionally, sachet, the grooves, film or cup maycontain a moisture regulating formulation capable of maintaining thewater activity of the instant coffee or other food product such asinstant tea, at an optimum level so that it is not too dry or too moistwhich can affect the extractability of the flavor elements.

The container may be provided with an oxygen absorbent film or othersorbent film that is in cup 42. The film may be cast, laminated orextrusion coated into the cup or preformed and attached to the cup byadhesives, ultrasonic sealing, or heat sealing. The oxygen absorbentfilm may consist of multilayer structure in which the oxygen absorbentis in the inner layers of the structure. The film may be provided withan abrasion resistant layer or a slippery layer, not shown, that willprovide abrasion resistance or slippage so that the filter's movementwill not be able to remove the oxygen absorbent (scavenger) materialsfrom the film. The resistance or slippage layer may be formed ofpolyethylene, polypropylene, polyamide and their copolymers.Conventional slip additives may be added into the layer that contactsthe coffee to result in a coefficient of friction of 0.5 or below,preferably 0.3 or below. While described with reference to an oxygenabsorbing film, it is possible that the film only contain CO₂ absorbingmaterials, or water absorbing materials. It is further possible that itcontain a combination of carbon dioxide, oxygen absorbing, and waterabsorbing materials.

The oxygen scavenger or other gas absorber may be placed in cup 42 by avariety of techniques, but an extrusion technique, such is utilized forhot melt adhesive is quick and may be done during manufacturing prior tothe support 40 being put in the cup. The extrusion materials include hotmelt polymers as well as plastisol materials discussed above that wouldcure in place.

Any suitable resin may be utilized in the invention for the carrier andthe absorbent film polymer that holds the oxygen scavenger, carbondioxide absorbent, water vapor absorber, or other sorbent. The polymerholds the sorbent so that it will not be carried into the instantcoffee, cocoa, or other food product when the container is used.Polymers useful for making the oxygen scavenging and absorbent articlescan include common polyolefins such as low-density polyethylene (LDPE),high-density polyethylene (HDPE), polypropylene (PP), polystyrene (PS),high impact polystyrene (HIPS), polycarbonates (PC), poly(methylmethacrylate) (PMMA) and their derivatives or copolymers.

Polymers suitable for the invention container and carriers andbiodegradable include common polymers generated from renewable resourcesand biodegradable polymers such as polylactic acid copolymers, starchbased polymers such as thermoplastics starch, polyhydroxyalkanoate(PHA), polyhydroxybutyrate (PHB). Biodegradable polymers that arepetroleum based such as polyethylene oxide, polyvinyl alcohol (PVOH) arealso included.

The invention uses common plastic article fabrication processes thatinclude extrusion, injection molding, extrusion coating, lamination,tableting and compounding to form the sorbent structures includingoxygen scavengers, CO₂ absorbers, and moisture regulators.

The oxygen scavenging fabricated article may contain moisture regulatorsbased upon silica gel, molecular sieve, activated carbon, clay or otherminerals. The compounds may contain various levels of water to achievewater activities ranging from 0.01 to 0.85. In the event that onlyprotection from deterioration of the mammal ingestible material byaction of water vapor is desired the n the absorber and moistureregulator silica gel, molecular sieve, activated carbon, clay, or otherminerals may be used without the oxygen scavenger or carbon dioxideabsorber. Silica gel is preferred as it is low in cost, effective, andsafe. Moisture absorbent materials such as disclosed in U.S. Pat. No.5,322,701—Cullen, herein incorporated by reference, could be placed intocontainers to enable longer storage of moisture sensitive materials.

The film/tape/ribbons for use in cup 42 of the invention may be a singleor multilayer films that are porous or solid, and consisting ofiron-based oxygen scavengers and electrolytes, such as disclosed inco-assigned U.S. patent application Ser. No. 12/416,685, filed Apr. 1,2009, hereby incorporated by reference. The film optionally consists ofmoisture regulators with a chosen water activity. Multilayer film ispreferred with at least one of water vapor absorber, carbon dioxideabsorber, or oxygen scavenger embedded inside the film and not exposedon film surface. Films with some porosity or voids are preferred tofacilitate the rate of absorption. Moisture regulator can beincorporated into the film during extrusion or from post-extrusionprocessing.

The following examples are used to illustrate some parts of theinvention. The Examples are illustrative and not exhaustive of theembodiments of the invention. Parts and percentages are by weight unlessotherwise indicated. The examples use ground coffee as the test materialto show the oxygen scavenging effectiveness. As they are effective withground coffee, they will also be effective in the container of theinstant invention.

Example 1 Oxygen Scavenging Films Packaged with Coffee

An extruded film that contained oxygen scavenger formulations wasprepared by following a method described in co-assigned U.S. patentapplication Ser. No. 12/416,685, filed Apr. 1, 2009, hereby incorporatedby reference, to test the oxygen scavenging behavior with the presenceof coffee. The film was extruded from a mixture of 17/3/80 weight ratioof iron, sodium chloride and low density polyethylene from a filmextrusion process. The materials were pre-mixed in a container and fedinto a twin screw extruder with the extruder and die temperatures set at220° C. Films, approximately 9 mil thick, were extruded from a 6″ dieand collected on a spool. The 9 mil film samples, cut in approximately1″ square pieces, were moisturized by placing drops of water on thesurface of the film and blotted to remove dripping water. The films wereplaced in 7″×7″ plastic barrier bags with a package of approximately 8.8gm ground coffee sealed in Tyvek breathable film bag. The barrier bagwas hot sealed and injected with 150 cc O₂/N₂ mixture to reach aninitial oxygen concentration of 3% or lower. The oxygen scavenging ratewas measured by using MOCON PacCheck Model 450 Head Space Analyzer.

Example 1A Coffee without Oxygen Scavenger

As a control, a separate barrier bag that consists of approximately 8.8gm ground coffee removed from a container, conditioned in ambienttemperature and environment for more than one hour, was sealed in Tyvekbreathable film bag without scavenger, and was tested for oxygenconcentration change over the same time period.

FIG. 24 shows the results of oxygen concentration change with time fortwo different scavenger loadings. The oxygen scavenging rate increaseswith the net amount of the scavengers used. In 88 hrs, a sample with astarting O₂ of 1.98% dropped to 0.04% with 0.52 gm of the scavenger inthe film. A sample of 2.21% O₂ dropped to 1.08% with 0.17 gm of thescavenger in the film. The 02 concentration of a sample with coffeepacket only without scavenger dropped from 2.45% to 2.37% with somevariation over the same time period. This example demonstrated that thescavenger gives much higher oxygen absorption rate than the combinationof coffee and the background materials. The oxygen scavenging capabilitycan be adjusted by the amount of the scavenger used and the preparationmethod adopted.

Example 2 Oxygen Scavenging Film Laminated on Coffee Lidding

Oxygen scavenging film was extruded with a mixture of 5.1/0.9/94 weightratio of iron/NaCl/PLA in which PLA was NatureWorks PLA 2002D resin. Theiron is the same as in Example 1. The composition of poly (lactic acid)resin (PLA) was pre-dried in a desiccant oven at 60° C. for at least 4hrs before extrusion. The mixture was extruded in a twin screw extruderto make 4″ wide and 4 mil thick films. A coffee lidding foil film peeledfrom a Green Mountain 55 cc cup coffee was used for lamination test. DowChemical Integral™ 801 adhesive film was used as an adhesive forlamination test. The extruded Fe/PLA film was stacked with the Integralfilm and the lidding film to form Fe/PLA-adhesive-lidding sandwichstructure. The structure was heat pressed in a heat sealer to form anoxygen-scavenging lidding structure.

Example 3 Oxygen Scavenging Sachet Packaged with Coffee

Packets with an approximate size of 1″×0.5″ made of a polyolefin filmcontaining iron-based oxygen scavenging formulation and moistureregulator were used for the test. The packets contained iron-basedscavenger and a moisture retaining material patented by MultisorbTechnologies. The packet consists by weight of approximately 40% iron,10% NaCl, 50% silica gel and some moisture. The packets had a wateractivity in the range of 0.4-0.8. The packets were stored with coffee in150 cc barrier bag and tested as described in Example 1. The oxygenabsorption property was measured by using MOCON PacCheck Model 450 HeadSpace Analyzer. FIG. 25 shows the oxygen scavenging result thatdemonstrated that the oxygen concentration decreased rapidly with time.The scavenging rate is much faster than the oxygen absorption rate ofthe coffee and the background material as shown in Example 1.

Example 4 Oxygen Scavenging Acrylic Coating Preparation

An acrylic emulsion was made using Neocryl A-5117 from Zeneca Resins. Aformulation comprising 50 weight percent of this acrylic emulsion and 50weight percent of a 200 mesh electrolytic iron reduced iron containing 2weight percent sodium chloride was coated on eight square inches of apolypropylene substrate and dried with heat. The coat weight was 0.0135grams per square inch. This oxygen absorbing coating was then placedinside of a test vessel with 500 cc of air or 100 cc of oxygen alongwith 2 square inches of a moisture saturated blotter paper. Threesamples were tested.

Sample 1 Sample 2 Sample 3 Composition weight 1.47 grams 1.71 grams 1.51grams CC of oxygen absorbed after 13. 16. 15. 48 hours CC of oxygenabsorbed after 13. 18. 15. 114 hours

Example 5 Oxygen Scavenging Polyvinyl Acetate Coating Preparation

A polyvinyl acetate in water emulsion was made using Vinac XX-210 fromAir Products. Forty three weight percent of this polyvinyl emulsion wascombined with 57 weight percent iron blend containing 200 meshelectrolytic reduced iron powder containing 2 weight percent of sodiumchloride. This formulation was then coated on to eight square inches ofa polypropylene substrate with a coat weight of 0.026 grams per squareinch. The resulting coating was then placed inside of a test vessel with500 cc of air or 100 cc of oxygen. A moisture source was also placedinside of the test vessel along with the sample. Three samples weretested.

Sample 1 Sample 2 Sample 3 Composition weight 1.47 grams 1.71 grams 1.51grams CC of oxygen absorbed after 22. 22. 22. 48 hours CC of oxygenabsorbed after 25. 25. 25. 114 hours

Example 6 Extruded Carbon Dioxide Scavenging Sheets

VitaCal-H calcium hydroxide (Ca(OH)₂) powder was obtained fromMississippi Lime Company. The as received powder was mixed with groundsilica gel (SG) powder that had a mean particle size of approximately 6micron with a by weight mixture ratio of VitaCal-H/SG=75/25. The mixturewas then blended with Petrothene GA502024 low density polyethylene resinobtained from LynodellBasell Industries to achieve the following blendweight ratios: Ca(OH)₂/SG/LDPE=30/10/60 and 40/10/50

The blends were extruded in a single screw extruder with a flat sheetdie attached to the extruder to make sheet materials. SAFOAM FPN3-40obtained from Reedy International Co. was added in some runs to makesamples that contained some voids or porosity. The extruder was set at160-220° C. temperature range and the die was at 220° C. The extrudedsheets, approximately 30-40 mil thick, were air cooled and winded on aroll.

Samples, approximately 0.4-0.7 grams were cut from the extruded sheetsand used for carbon dioxide scavenging test. The samples werepre-hydrated with water to obtain approximately 1 to 5% water contentdetermined by weight gain. The samples were then sealed in foil pouchesfilled with 600 cc gas that contained approximately 25-20% carbondioxide balanced with nitrogen. The concentration of carbon dioxide wasmeasured using a MOCON model 333 Pac-Check analyzer for various periodsof time. The scavenging test data in terms of cc of CO2 absorbed isshown in Table-1. The formulations listed are weight ratios ofCa(OH)₂/SG/LDPE. Safoam was added as additional percentage. The datashowed that carbon dioxide was absorbed effectively with the increase oftime from 24-72 hrs.

TABLE 1 CO₂ absorption of extruded sheets CO₂ absorbed, cc Safoam+,Weight, 0 24 48 72 ID Formulation* %** gm hrs hrs hrs hrs 1 30/10/60 50.69 0 6.82 12.7 17.2 2 30/10/60 2 0.66 0 6.94 12.8 20.1 3 40/10/50 00.57 0 7.7  12.9 20.6 4 40/10/50 5 0.48 0 9.96 11.2 17.8 *Formulationratio = Ca(OH)₂/SG/LDPE by weight **Percent by weight of formulation+safoam FPN 3-40 at hydrofluocarbon

Example 7 Injection Molded Carbon Dioxide Scavenging Discs

Ca(OH)₂ and silica gel used were the same as that of Example 7.Solka-floc wood fiber was obtained from International Fiber Company.Polypropylene was Sunoco CP360H resin, an elastomer Kraton G1657 wasobtained from Kraton Polymers. These materials were blended to form thefollowing material weight ratios: Ca(OH)₂/SG/Solka-floc/PP/Kraton1657=48/6/6/36/4

The materials were compounded in a twin screw compounding machine at200-250 C temperature and extruded into strands, cooled in water andpelletized. The compounded pellets were injection molded in a singleshot injection molding machine to form 1.3″ diameter discs. The discswere tested for carbon dioxide scavenging performance following theprocedure described above. The test data showed that the discs graduallyabsorbed carbon dioxide with the test time. The absorbing rate was foundincreased when the disc surfaces were roughened with a sand paper priorto hydration. Table-2 shows the data of an injection molded disc, sandedand hydrated with 1% water prior to test.

TABLE 2 CO₂ absorption of injection molded discs Disc CO₂ absorbed, ccweight, % 0 96 120 144 ID gm hydration hrs hrs hrs hrs Sanded 1.2 1.0 025.7 27.5 29.9 disc

Example 8 Coated Carbon Dioxide Scavenging Paperboard

Coating formulations were prepared by using the same sorbent ingredientsas described above. Luvitec K30 (BASF) polyvinylpyrrolidone (PVP) andpolyethylene glycol 6000 (Aldrich Chemical) were used to make thecoating solutions. PVP was dissolved in water to form a 17 wt %solution. PEG was dissolved in water to form a 48 wt % solution. Bothsolutions were clear and without residues. A mixture of the PEG and PVPsolutions was made with 90/10 ratio to achieve a resin content ofapproximately 45% in water. The solutions were used to mix with Ca(OH)₂and SG to form a coating solution that has the following coatingformulation: Ca(OH)₂/SG/(PEG/PVP)=40/10/50

The solutions were coated on an 20 mil paperboard substrate and dried inoven at 115 C for more than 2 hours to remove the water. The coatedsamples were cut and hydrated with wet sponge to be used for carbondioxide scavenging test by using the same test method described above.The test data is shown in Table-3. It is seen that carbon dioxide wasabsorbed rapidly over the test time period.

TABLE 3 CO₂ absorption of Ca(OH)₂-coated paperboard coupons 0 hrs 24 hrs96 hrs ID Coating weight, gm % hydration CO₂ absorbed, cc 100710-1 1.211.2 0 4.8 27.1 100710-2 1.44 4.0 0 15.8 50.5

Another coating solution was prepared by dissolvinghydroxypropylcellulose resin (Hercules Klucel EF) in water to form auniform solution. Ca(OH)₂ and SG were mixed with the solution to form apaste formulation approximately Ca(OH)₂/SG/Klucel=70/10/20 weightratios. Klucel served as a binder for the solid formulation. The pasteformulation was pressed on the same paperboard and dried to form aporous coating. The pressed-coating, although brittle, maintainedintegrity for test. It was hydrated with wet sponge and the weight gainwas recorded. This high solid loading sample was tested for CO₂scavenging performance. The data in Table-4 showed that CO₂ was absorbedrapidly over the test time period with high absorption capacity.

TABLE 4 CO₂ absorption of Ca(OH)₂-coated paperboard with high solidloading 0 hrs 24 hrs 336 hrs ID Coating weight, gm % hydration CO₂absorbed, cc 093010-1 0.52 5 0 67.3 86.8

Example 9 Capsule Filled with Carbon Dioxide Absorber Blend

Plastic capsules were hand filled with Multisorb Technologies CO₂absorbing formula (semi-dry flow able granules) to achieve a CO₂ freeenvironment. The capsules are breathable, semi-rigid, and are partiallyresistant to hot water. The device (capsule) provides for a timedabsorption of CO₂ from coffee filled pods stored at varioustemperatures. The CO₂ capsule limits the expansion of a non-breathablecup (from CO₂ emissions from coffee) and also enhances or maintains thearomas and oils of the freshly roasted coffee powders and granules. Theformulation enclosed in the capsules were Ca(OH)₂/SG=67/33 ratio withthe silica gel containing water. The net formulation wasCa(OH)₂/SG/H2O=67/20/13 weight ratio. The blend was in loose powderformat contained in the capsule. The CO₂ scavenging data is shown inTable-5.

TABLE 5 CO₂ absorption of Ca(OH)₂ filled capsule 0 hrs 72 hrs 240 hrs IDCoating weight, gm % hydration CO₂ absorbed, cc Caplug 0.65 30 0 32.636.4

Example 10 Tablets Made of CO₂ Scavengers

The formulation used in Example 10 was compressed into tablets in a moldon a conventional cold or hot pressing machine. The tablets were thencoated with polyethylene powders on the surface. The coated tablets wereheated in a heating chamber at a temperature below the melting point ofpolyethylene but hot enough to fuse the coated powder particles. Thecoated tablets were conditioned at room temperature in 80% relativehumidity environment for 16 hrs. The tablets showed CO₂ scavengingproperties as listed in Table-6.

TABLE 6 CO₂ absorption of Ca(OH)₂ filled tablets Coating % CO₂ absorbed,cc weight, hydra- 0 24 48 72 ID gm tion hrs hrs hrs hrs 5%-S2 0.85 5 011.3 14.9 17.3

Example 11 Sintered Structure Carbon Dioxide Scavenging Disc/Component

Ca(OH)₂ and silica gel used were the same as that of Example 7.Solka-floc wood fiber was obtained from International Fiber Company.Polypropylene was Sunoco CP360H resin, an elastomer Kraton G1657 wasobtained from Kraton Polymers. These materials were blended to form thefollowing material weight ratios: Ca(OH)₂/SG/Solka-floc/PP/Kraton1657=48/6/6/36/4

The materials were compounded in a twin screw compounding machine at200-250 C temperature, cooled in water and pelletized. The pellets willthen be ground to relatively small particle size which will then exposeportions of the active ingredients. This exposure will increase theadsorption rate. The ground active material is then fused together underheat and pressure which is applied to the material in a mold. Theresults are a porous sintered structure that increased active surfacearea.

Example 12

A gas permeable polyethylene film sachet container is filled with 1.1 gof calcium hydroxide of 200 mesh and 1.1 g of silica gel in a 2:1 blendwith water. The sachet is sealed and placed into a shrink wrap packageof 4 ounce of Swiss cheese using conventional grocery cheese wrappackaging techniques. After four months storage at about 40° F. thecheese exhibits good color and taste. Further, the package is notexpanded.

Example 13

This example illustrates the rapid acting of the calcium hydroxide inabsorption of carbon dioxide.

As a control sachets containing calcium oxide an amount of 1.1 g and 0.9g of white porous silica gel and water in a 2:1 ratio are formed. Thesachets are each placed into an impermeable bag that is filled with 300cm³ of a bout a 30% by weight carbon dioxide and oxygen gas mix. Thethree samples are sampled at two hours, four hours, six hours, 24 hours,48 hours and 72 hours. The results are illustrated in Table 1 below

TABLE 1 Initial CO₂ % 2 hrs 4 hrs 6 hrs 24 hrs 48 hrs 72 hrs S1 27.528.4 27.2 27.2 27.0 26.6 26.2 S2 26.5 26.4 26.3 26.1 26.0 25.7 25.5 S326.9 26.7 26.2 26.6 25.8 Flat 25.6 25.8

Three sachets containing 1.1 g of calcium hydroxide (200 mesh) and 1.1 gof a mixture of water and silica gel in a 2:1 ratio are formed. Thesachets are placed in a bag containing carbon dioxide as indicated abovefor the calcium oxide test and are sampled two hours and 24 hours. Theresults are illustrated in Table 2 below:

TABLE 2 Ca(OH₂)₂ Calcium Hydroxide (Lab), HWPSG Initial 2 hrs 24 hrs S125.5 21.6 19.3 S2 25.7 22.1 18.0 S3 25.8 22.1 19.9

As may be seen from the comparison of Table 1 and Table 2 there is amuch faster pickup of the carbon dioxide by the calcium hydroxide. Thisis shown by the rapid decrease in carbon dioxide left in the bag.

The materials of the above Examples 1-13 may be utilized in theinvention as scavengers or absorbents. Water vapor absorbers could bemade by similar techniques using silica gel and molecular sievematerials.

A further embodiment of the invention focuses on instances where theabsorber will be used in high carbon dioxide concentration environmentsand there is a need for a rapid absorption of headspace oxygen. In theseinstances the purpose of the carbon dioxide absorber is not necessarilyto absorb carbon dioxide, but to produce enough water to promote theoxygen absorption reaction. A typical example of this would be ininstances where oxygen sensitive products are placed in the barriercontainers that are gas flushed with high concentrations of carbondioxide. While gas flushing removes most of the ambient oxygen, smallamounts of oxygen still remain in the packaging, which could bedetrimental to the meat product. Therefore desirable to remove thisheadspace oxygen to prevent degradation of the product.

Typically this is done with an oxygen scavenger that has had additionalwater added to accelerate the reaction. This is not necessarilydesirable as exposure to oxygen prior to insertion or during thepackaging process can cause these highly reactive absorbers to startabsorbing oxygen and lose most of their potency before it is needed. Toremedy this, a water generating composition that generates water byreacting a carbon dioxide, such as calcium hydroxide, can be added tooxygen absorbers that are intended to be placed in high carbon dioxideenvironments. In these instances the carbon dioxide absorber wouldgenerate the water needed to promote the oxygen absorber. This is evenoperable in instances where an immediate pickup is desired and watermust be added to the sachet. In those instances just enough water can beadded to the sachet to keep the overall water activity of thecomposition below what is required to promote the oxygen absorber. Thewater generating composition can then generate just enough water to putthe overall water activity of the absorber into a range where the oxygenabsorbing composition can react with the ambient oxygen. To prevent theabsorber from the absorbing oxygen prematurely by accidentally pickingup ambient moisture, the sachet itself can be made with material that isimpermeable to water and water vapor, but permeable to carbon dioxideoxygen. Olefins are a preferred material for this, including but notlimited to polyethylene and polypropylene, but any material that metthis requirement would be acceptable.

An extension of this would be in using this same a method for oxygenabsorbing films. In these instances, the water generating compositionand oxygen absorbing composition would be compounded with a resin thatis permeable to oxygen and carbon dioxide but not necessarily permeableto water or water vapor. From this composition if you could be made toany conventional film manufacturing means. This film could be used in amultilayer scheme in which one of the layers is impermeable to oxygen.This this would create an ideal oxygen barrier film to be used with highcarbon dioxide environments, as oxygen ingress would be prevented by thebarrier layer, and any head space oxygen would be absorbed by the layercontaining the oxygen absorber and water generating composition.

The invention has been described in detail with particular reference toa presently preferred embodiment, but it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention. The presently disclosed embodiments are thereforeconsidered in all respects to be illustrative and not restrictive. Thescope of the invention is indicated by the appended claims, and allchanges that come within the meaning and range of equivalents thereofare intended to be embraced therein.

1. A method of absorbing carbon dioxide and oxygen, comprising: disposing a carbon dioxide absorber and an oxygen scavenger within a container containing a product, wherein the product gives off carbon dioxide and is degradable in the presence of oxygen; sealing the container to form a sealed container containing the carbon dioxide absorber, the oxygen scavenger, and the product; absorbing, with the carbon dioxide absorber, carbon dioxide given off by the product within the container, wherein absorption of the carbon dioxide by the carbon dioxide absorber produces water; and at least partially promoting the oxygen absorption of the oxygen scavenger with the water.
 2. The method of claim 1, wherein at least one of the carbon dioxide absorber and the oxygen scavenger is contained within a sachet, the method further including disposing the sachet within the container before sealing the container.
 3. The method of claim 2, wherein the sachet is formed from at least one of a carbon dioxide permeable material, an oxygen permeable material, and a water vapor permeable material.
 4. The method of claim 2, wherein the sachet contains between approximately 38 percent by weight and approximately 66 percent by weight of the carbon dioxide absorber, with the remainder being the oxygen scavenger.
 5. The method of claim 1, wherein the carbon dioxide absorber comprises calcium hydroxide.
 6. The method of claim 1, wherein the oxygen scavenger comprises silica gel.
 7. A sealed container, comprising: an inner cavity; a product disposed within the inner cavity, the product giving off carbon dioxide and being degradable in the presence of oxygen; a carbon dioxide absorber disposed within the inner cavity and configured to absorb carbon dioxide given off by the product within the container, wherein absorption of carbon dioxide by the carbon dioxide absorber produces water; and an oxygen scavenger disposed within the inner cavity and arranged to receive the water, wherein the water at least partially promotes the oxygen scavenger.
 8. The container of claim 7, wherein the container is formed from a material that is substantially impermeable to carbon dioxide, oxygen, and water.
 9. The container of claim 7, further including a sachet containing at least one of the carbon dioxide absorber and the oxygen scavenger, wherein the sachet is formed from at least one of a carbon dioxide permeable material, an oxygen permeable material, and a water vapor permeable material.
 10. The container of claim 7, wherein the product comprises at least one of cheese, kimchi, and ground coffee.
 11. The container of claim 7, wherein the carbon dioxide absorber comprises calcium hydroxide having a grain size of between approximately 200 millimeters and approximately 300 millimeters.
 12. The container of claim 11, wherein the calcium hydroxide is embedded in a film.
 13. The container of claim 7, wherein the carbon dioxide absorber is embedded in a film, and the film is disposed within the inner cavity.
 14. A sealed container, comprising: a gas flushed inner cavity wherein the flush gas comprises at least carbon dioxide; a product disposed within the inner cavity that is sensitive to oxygen; a water producing carbon dioxide absorber, disposed within the inner cavity and configured to absorb carbon dioxide from the flush gas within the container, wherein absorption of carbon dioxide by the carbon dioxide absorber produces water; and an oxygen scavenger disposed within the inner cavity and arranged to receive the water, wherein the water at least partially promotes the oxygen scavenger.
 15. A method of absorbing oxygen without prematurely promoting scavenging of oxygen comprising: disposing a water producing carbon dioxide absorber and an oxygen scavenger within a container containing a product; gas flushing the container with a flushing gas that contains carbon dioxide sealing the container to form a sealed container containing the carbon dioxide absorber, the oxygen scavenger, the flushing gas, and the product; absorbing, with the carbon dioxide absorber, carbon dioxide from the flushing gas, wherein absorption of the carbon dioxide by the carbon dioxide absorber produces water; and at least partially promoting the oxygen absorption of the oxygen scavenger with the water.
 16. The method of claim 15 further comprising disposing a carbon dioxide absorber and the oxygen scavenger within a oxygen impermeable container.
 17. A oxygen absorbing device comprising: A water generating composition comprising a carbon dioxide absorber; an oxygen scavenger that will react with water to absorb oxygen; an outer container containing the water generating composition and the oxygen scavenger.
 18. The oxygen absorbing device of claim 17 where the water generating composition comprises calcium hydroxide.
 19. The oxygen absorbing device of claim 17 where the oxygen scavenger comprises a mixture of iron and an electrolyte.
 20. The oxygen absorbing device of claim 17 where the outer container comprises a material that is permeable to oxygen and carbon dioxide but impermeable to water vapor and liquid water.
 21. The oxygen absorbing device of claim 20 wherein the outer container comprises an olefin.
 22. The oxygen absorbing device of claim 21 wherein the olefin is selected from the group consisting of polyethylene, polypropylene, and copolymers thereof.
 23. The oxygen absorbing device of claim 17 further comprising water sufficient enough to raise the oxygen absorbing compositions water activity to just below what is needed to initiate a redox reaction.
 24. An oxygen absorbing film comprising: a first layer comprising an oxygen and carbon dioxide impermeable resin; a second layer comprising a resin that is permeable to oxygen and carbon dioxide, an oxygen scavenging composition, and a water generating composition comprising a carbon dioxide scavenger. 